JP2010229571A - Method and apparatus for papermaking - Google Patents
Method and apparatus for papermaking Download PDFInfo
- Publication number
- JP2010229571A JP2010229571A JP2009075650A JP2009075650A JP2010229571A JP 2010229571 A JP2010229571 A JP 2010229571A JP 2009075650 A JP2009075650 A JP 2009075650A JP 2009075650 A JP2009075650 A JP 2009075650A JP 2010229571 A JP2010229571 A JP 2010229571A
- Authority
- JP
- Japan
- Prior art keywords
- starch
- papermaking process
- process water
- fine particles
- functional group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 229920002472 Starch Polymers 0.000 claims abstract description 88
- 235000019698 starch Nutrition 0.000 claims abstract description 88
- 239000008107 starch Substances 0.000 claims abstract description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000010419 fine particle Substances 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000000701 coagulant Substances 0.000 claims abstract description 30
- 125000000524 functional group Chemical group 0.000 claims abstract description 30
- 125000002091 cationic group Chemical group 0.000 claims abstract description 16
- 229920000620 organic polymer Polymers 0.000 claims abstract description 14
- 125000000129 anionic group Chemical group 0.000 claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000002351 wastewater Substances 0.000 abstract description 15
- 230000002829 reductive effect Effects 0.000 abstract description 7
- 239000004382 Amylase Substances 0.000 description 17
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- 235000019418 amylase Nutrition 0.000 description 17
- 238000007792 addition Methods 0.000 description 15
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- 239000008103 glucose Substances 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
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- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
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- PORQOHRXAJJKGK-UHFFFAOYSA-N 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone Chemical compound CCCCCCCCN1SC(Cl)=C(Cl)C1=O PORQOHRXAJJKGK-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Paper (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Sorption (AREA)
Abstract
Description
本発明は、紙の製造工程から排出される廃水のCODを低減するための製紙方法及び装置に関する。 The present invention relates to a paper manufacturing method and apparatus for reducing COD of wastewater discharged from a paper manufacturing process.
紙の製造工程には、古紙の塗工層由来の澱粉、段ボール古紙の糊由来の澱粉、紙力増強剤として使用されている澱粉、層間接着剤として使用されている澱粉など多量の澱粉が含まれている。これらの澱粉を栄養源として細菌等の微生物が増殖すると、配管やタンクの壁面、フィルター上などにスライムと呼ばれる生物膜が形成され、抄紙工程における生産性低下や紙質劣化などのスライム障害が引き起こされる。 The paper manufacturing process includes a large amount of starch, such as starch derived from the used paper coating layer, starch derived from paste from used corrugated paper, starch used as a paper strength enhancer, and starch used as an interlayer adhesive. It is. When microorganisms such as bacteria grow using these starches as nutrients, biofilms called slimes are formed on the walls of walls, pipes, tanks, etc., causing slime problems such as reduced productivity and paper quality degradation in the papermaking process. .
スライム中の微生物は、澱粉分解酵素であるアミラーゼを産生する能力が高い細菌によって占有されている。アミラーゼは、スライムから製紙工程水に放出されて、パルプ繊維に吸着している澱粉や、水中に分散している不溶性の澱粉粒子をグルコースへと加水分解し、ギ酸、乳酸、酢酸、酪酸などの有機酸を生成する。 Microorganisms in the slime are occupied by bacteria having a high ability to produce amylase, which is an amylolytic enzyme. Amylase is released from the slime into the papermaking process water and hydrolyzes the starch adsorbed on the pulp fibers and the insoluble starch particles dispersed in the water into glucose, such as formic acid, lactic acid, acetic acid and butyric acid. Produces organic acids.
このようなスライム中の微生物のアミラーゼの働きは、製造工程からの廃水における澱粉及び澱粉に由来するグルコースや有機酸などのCOD成分の増加の原因となり、廃水処理コストを増大させる要因となっている。また、アミラーゼの働きによって、紙の強度や印刷適性等を向上させる機能を有する澱粉がパルプスラリー中から消失する結果、新たに澱粉を添加、噴霧、塗工する必要が生じ、製造コストの増大にもつながっている。 The action of the microbial amylase in the slime causes an increase in starch and the COD components such as glucose and organic acids derived from the starch in the wastewater from the manufacturing process, and increases the wastewater treatment cost. . In addition, as a result of the disappearance of the starch having the function of improving the strength and printability of paper due to the action of amylase from the pulp slurry, it becomes necessary to newly add, spray, and coat, resulting in an increase in production cost. Is also connected.
特許文献１には、「澱粉が紙原料中に添加される紙の製造方法において、前記製造工程の所定箇所においてアミラーゼ活性の測定を行い、その測定値に基づいてスライムコントロール剤の添加を行う紙の製造方法」が開示されている。この製造方法によれば、スライム障害による澱粉使用紙の品質劣化等を防止することができる。また、特許文献２〜５には、スライムコントロール剤が提案されている。 Patent Document 1 states that “in a paper manufacturing method in which starch is added to a paper raw material, amylase activity is measured at a predetermined location in the manufacturing process, and a slime control agent is added based on the measured value. Is disclosed. According to this manufacturing method, it is possible to prevent deterioration of the quality of the starch-using paper due to slime failure. Patent Documents 2 to 5 propose slime control agents.
近年、紙の強度や印刷適性を安価に維持するために、紙力増強剤や表面強度増強剤としての澱粉の使用が急増している。さらに、澱粉を多く含む古紙の利用率も高まっている。そのため、澱粉及び澱粉分解物に由来する廃水への負荷が高くなり、廃水処理コストの増大という問題が一層顕在化してきている。 In recent years, the use of starch as a paper strength enhancer or a surface strength enhancer has been rapidly increasing in order to maintain the strength and printability of paper at a low cost. Furthermore, the utilization rate of waste paper containing a large amount of starch is also increasing. For this reason, the load on waste water derived from starch and starch degradation products has increased, and the problem of increased waste water treatment costs has become more apparent.
また、一定の紙質を得るために、スライム中の微生物のアミラーゼの働きによってパルプスラリー中から消失した澱粉を増添することが行われており、廃水への負荷を一層高めるとともに、製造コストを増大させることとなっている。 In addition, in order to obtain a certain level of paper quality, starch that has disappeared from the pulp slurry is added by the action of microbial amylase in the slime, further increasing the burden on wastewater and increasing production costs. It is supposed to let you.
そこで、本発明は、廃水への負荷を低減し、かつ一定の紙質が得られる製紙方法を提供することを主な目的とする。 Thus, the main object of the present invention is to provide a papermaking method that can reduce the load on wastewater and obtain a certain level of paper quality.
上記課題解決のため、本発明は、澱粉を含有する製紙工程水にスライムコントロール剤を添加する工程と、前記製紙工程水にカチオン性官能基、アニオン性官能基又は水素結合能を持つ官能基を有する実質的に水不溶性の有機系微粒子を添加する工程と、有機系微粒子の添加後の製紙工程水に無機凝結剤、有機凝結剤及び有機高分子凝集剤から選択される１以上を添加する工程と、を含む製紙方法を提供する。
この製紙方法では、スライムコントロール剤によって澱粉の分解を抑制し、有機系微粒子によって澱粉を吸着し、澱粉を吸着した有機系微粒子を凝集させて澱粉を紙製品に定着させることで、廃水に持ち込まれる澱粉量を低減することができる。
併せて、本発明は、澱粉を含有する製紙工程水にスライムコントロール剤を添加する手段と、前記製紙工程水にカチオン性官能基、アニオン性官能基又は水素結合能を持つ官能基を有する実質的に水不溶性の有機系微粒子を添加する手段と、澱粉吸着工程後の製紙工程水に、無機凝結剤、有機凝結剤及び有機高分子凝集剤から選択される１以上を添加する手段と、を備える製紙装置を提供する。
In order to solve the above problems, the present invention includes a step of adding a slime control agent to papermaking process water containing starch, and a functional group having a cationic functional group, an anionic functional group, or a hydrogen bonding ability in the papermaking process water. A step of adding substantially water-insoluble organic fine particles, and a step of adding one or more selected from an inorganic coagulant, an organic coagulant and an organic polymer flocculant to the papermaking process water after the addition of the organic fine particles And a papermaking method including:
In this papermaking method, the decomposition of starch is suppressed by the slime control agent, the starch is adsorbed by the organic fine particles, the organic fine particles adsorbing the starch are agglomerated, and the starch is fixed on the paper product, which is brought into the wastewater. The amount of starch can be reduced.
In addition, the present invention includes a means for adding a slime control agent to papermaking process water containing starch, and a material having a cationic functional group, an anionic functional group, or a functional group having hydrogen bonding ability in the papermaking process water. Means for adding water-insoluble organic fine particles, and means for adding at least one selected from an inorganic coagulant, an organic coagulant and an organic polymer flocculant to the papermaking process water after the starch adsorption process. A papermaking apparatus is provided.
本発明おいて、「澱粉」は、例えばカチオン化澱粉、両性澱粉、アルファ化澱粉、エステル化澱粉等の加工澱粉を包含し、狭く限定されないものとする。 In the present invention, “starch” includes, for example, processed starch such as cationized starch, amphoteric starch, pregelatinized starch, esterified starch, and the like, and is not limited narrowly.
本発明により、廃水への負荷を低減し、かつ一定の紙質が得られる製紙方法が提供される。 The present invention provides a papermaking method that reduces the load on wastewater and that provides a certain level of paper quality.
以下、本発明を実施するための好適な形態について説明する。なお、以下に説明する実施形態は、本発明の代表的な実施形態の一例を示したものであり、これにより本発明の範囲が狭く解釈されることはない。 Hereinafter, preferred embodiments for carrying out the present invention will be described. In addition, embodiment described below shows an example of typical embodiment of this invention, and, thereby, the range of this invention is not interpreted narrowly.
本発明に係る製紙方法は、澱粉を含有する製紙工程水にスライムコントロール剤を添加する工程（分解抑制工程）と、製紙工程水にカチオン性官能基、アニオン性官能基、又は水素結合能を持つ官能基を有する実質的に水不溶性の有機系微粒子を添加する工程（吸着工程）と、有機系微粒子の添加後の製紙工程水に無機凝結剤、有機凝結剤及び有機高分子凝集剤から選択される１以上を添加する工程（凝集工程）とを含む。分解抑制工程では、製紙工程水へのスライムコントロール剤の添加によって、スライム中の微生物のアミラーゼの働きによる澱粉の分解を抑制する。続く吸着工程では、製紙工程水へ添加した有機系微粒子に澱粉を吸着させる。そして、凝集工程において、澱粉を吸着した有機系微粒子を凝集させて、製紙工程水中の澱粉を紙製品に歩留まらせることで、廃水に持ち込まれる澱粉量を低減する。これにより、廃水中の澱粉及び澱粉分解物に由来する有機物成分の含有量を低減させ、廃水への負荷を軽減することができ、同時に得られる紙製品の強度や印刷適性等の品質を高めることができる。 The papermaking method according to the present invention has a step of adding a slime control agent to the papermaking process water containing starch (decomposition suppression process), and has a cationic functional group, an anionic functional group, or hydrogen bonding ability in the papermaking process water. The step of adding substantially water-insoluble organic fine particles having a functional group (adsorption step) and the paper making process water after the addition of organic fine particles are selected from inorganic coagulants, organic coagulants and organic polymer flocculants. And a step of adding one or more (aggregation step). In the decomposition inhibiting step, the addition of a slime control agent to the papermaking process water suppresses starch degradation due to the action of amylase of microorganisms in the slime. In the subsequent adsorption process, starch is adsorbed on the organic fine particles added to the papermaking process water. In the agglomeration step, the organic fine particles adsorbing the starch are agglomerated, and the starch in the papermaking process water is retained in the paper product, thereby reducing the amount of starch brought into the wastewater. As a result, the content of organic components derived from starch and starch degradation products in wastewater can be reduced, the load on wastewater can be reduced, and simultaneously the quality of paper products obtained, such as strength and printability, can be improved. Can do.
また、本発明に係る製紙装置は、澱粉を含有する製紙工程水にスライムコントロール剤を添加する手段と、製紙工程水にカチオン性官能基、アニオン性官能基又は水素結合能を持つ官能基を有する実質的に水不溶性の有機系微粒子を添加する手段と、澱粉吸着工程後の製紙工程水に無機凝結剤、有機凝結剤及び有機高分子凝集剤から選択される１以上を添加する手段とを備え、上記の製紙方法を実施可能な構成を有する。 Further, the papermaking apparatus according to the present invention has means for adding a slime control agent to papermaking process water containing starch, and has a cationic functional group, an anionic functional group, or a functional group having hydrogen bonding ability in the papermaking process water. Means for adding substantially water-insoluble organic fine particles, and means for adding one or more selected from inorganic coagulants, organic coagulants and organic polymer flocculants to the papermaking process water after the starch adsorption process The paper making method can be implemented.
以下、分解抑制工程、吸着工程及び凝集工程の各工程について詳細に説明する。 Hereinafter, each process of a decomposition | disassembly suppression process, an adsorption | suction process, and an aggregation process is demonstrated in detail.
１．分解抑制工程
本工程は、スライム中の微生物のアミラーゼによって、パルプ繊維に吸着している澱粉、及び製紙工程水中に分散している澱粉が分解されることを抑制する工程である。本工程では、スライム中の微生物のアミラーゼによる澱粉の分解を抑制するため、製紙工程水中にスライムコントロール剤を添加する。スライムコントロール剤の添加により、製造工程全域でのスライム増殖を製造期間中において抑え、アミラーゼによる澱粉分解を抑制することができる。
1. Decomposition suppression step This step is a step of suppressing the decomposition of starch adsorbed on pulp fibers and starch dispersed in papermaking process water by amylase of microorganisms in the slime. In this step, a slime control agent is added to the papermaking process water in order to suppress starch degradation by amylase of microorganisms in the slime. By adding the slime control agent, slime growth throughout the production process can be suppressed during the production period, and starch degradation by amylase can be suppressed.
スライムコントロール剤には、公知の化合物を用いることができるが、澱粉を分解しないスライムコントロール剤を選択することが必要である。具体的には、スライムコントロール剤には、2，2−ジブロモ−3−ニトリロプロピオンアミド、N−ブロモアセトアミドなどのブロモアミド系化合物、1，2−ビス（ブロモアセトキシ）エタン、1，4−ビス（ブロモアセトキシ）−2−ブテンなどのブロモ酢酸エステル系化合物、2−メチル−4−イソチアゾリン−3−オン、5−クロロ−2−メチル−4−イソチアゾリン−3−オン又はその金属塩、4，5−ジクロロ−2−オクチル−4−イソチアゾリン−3−オンなどのイソチアゾロン化合物、2−ブロモ−2−ニトロ−1，3−プロパンジオール、2，2−ジブロモ−2−ニトロエタノールなどのブロモニトロアルコール化合物とそのエステル、4，5−ジクロロ−1，2−ジチオラン−3−オン、3，3，4，4−テトラクロロテトラヒドロチオフェン−1，1−ジオキシドなどの環状イオウ化合物、メチレンビスチオシアネート、5−クロロ−2，4，6−トリフルオロイソフタロニトリル、オルトフタルアルデヒド、ジクロログリオキシム、5，5−ジメチルヒダントイン、N−クロロ−5，5−ジメチルヒダントイン、1−ブロモ−3−クロロ−5，5−ジメチルヒダントインなどのヒダントイン系化合物、酸化剤とアンモニウムとを混合することによって得られる反応物殺菌剤などを採用できる。なお、酸化剤としては、次亜塩素酸ナトリウム、次亜塩素酸カルシウム、1−ブロモ−3−クロロ−5，5−ジメチルヒダントインなどを例示でき、アンモニウム塩としては、臭化アンモニウム、硫酸アンモニウムなどを例示できる。これらのスライムコントロール剤は単独で、又は複数を組み合わせて用いることができる。 A known compound can be used as the slime control agent, but it is necessary to select a slime control agent that does not decompose starch. Specifically, the slime control agent includes 2,2-dibromo-3-nitrilopropionamide, bromoamide compounds such as N-bromoacetamide, 1,2-bis (bromoacetoxy) ethane, 1,4-bis ( Bromoacetate compounds such as bromoacetoxy) -2-butene, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one or metal salts thereof, 4,5 -Isothiazolone compounds such as dichloro-2-octyl-4-isothiazolin-3-one, bromonitroalcohol compounds such as 2-bromo-2-nitro-1,3-propanediol, 2,2-dibromo-2-nitroethanol And its esters, 4,5-dichloro-1,2-dithiolane-3-one, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and other rings Sulfur compound, methylene bis thiocyanate, 5-chloro-2,4,6-trifluoroisophthalonitrile, orthophthalaldehyde, dichloroglyoxime, 5,5-dimethylhydantoin, N-chloro-5,5-dimethylhydantoin, 1 -Hydantoin compounds such as bromo-3-chloro-5,5-dimethylhydantoin, reactant bactericides obtained by mixing an oxidizing agent and ammonium, and the like can be employed. Examples of the oxidizing agent include sodium hypochlorite, calcium hypochlorite, and 1-bromo-3-chloro-5,5-dimethylhydantoin. Examples of ammonium salts include ammonium bromide and ammonium sulfate. It can be illustrated. These slime control agents can be used alone or in combination.
スライムコントロール剤として最も好ましくは、酸化剤とアンモニウムとを混合することによって得られる反応物殺菌剤が使用される。かかる反応物殺菌剤によれば、製造工程全域のスライムを経済的にも安価にコントロールでき、直接澱粉を酸化分解することもない。 Most preferably, a reactant bactericidal agent obtained by mixing an oxidizing agent and ammonium is used as a slime control agent. According to such a reactant bactericide, slime throughout the production process can be controlled economically and inexpensively, and starch is not directly oxidatively decomposed.
スライムコントロール剤添加の管理は、製造工程全域で採取した製紙工程水中のアミラーゼ活性を定期的に、好ましくは連続的に測定して監視し、測定値が予め定めた閾値を越えた時に添加量を増やすように行うことが好ましい。閾値としては、特に限定されないが、例えば０．００２CU／gとすることができる。 The management of the addition of slime control agent is to monitor amylase activity in papermaking process water collected throughout the production process periodically, preferably continuously, and monitor the addition amount when the measured value exceeds a predetermined threshold. It is preferable to increase the number. Although it does not specifically limit as a threshold value, For example, it can be set to 0.002CU / g.
また、スライムコントロール剤添加の管理は、製紙工程水のORP（酸化還元電位）を定期的に、好ましくは連続的に測定することによってスライム増殖を監視し、測定値が予め定めた閾値を下回った時に添加量を増やすようにしてもよい。さらに、製紙工程水のORP値をプラスの好気条件に維持するようにスライムコントロール剤を添加して、嫌気条件で促進される微生物の澱粉分解を抑制するようにすることもできる。製紙工程水のORPを連続的に測定する場合には、強酸化剤の流入による澱粉の酸化的分解を把握することもできる。ORP値は、特に限定されないが、一般的には0〜＋500mVの範囲で維持することが好ましい。 In addition, the management of the addition of the slime control agent is to monitor the slime growth by measuring the ORP (redox potential) of the papermaking process water periodically, preferably continuously, and the measured value falls below a predetermined threshold. Sometimes the amount added may be increased. Furthermore, a slime control agent can be added so as to maintain the ORP value of the papermaking process water under a positive aerobic condition, thereby suppressing the starch degradation of microorganisms promoted under the anaerobic condition. When continuously measuring the ORP of papermaking process water, it is possible to grasp the oxidative degradation of starch due to the inflow of strong oxidizing agents. The ORP value is not particularly limited, but in general, it is preferably maintained in the range of 0 to +500 mV.
スライムコントロール剤の添加量及び添加回数は、特に限定されず、上述のアミラーゼ活性又はORPの測定による水質測定結果に基づいて適宜決定される。添加量及び添加回数は、例えば２〜５０mg／L、１〜４８回／日である。 The addition amount and the number of additions of the slime control agent are not particularly limited, and are appropriately determined based on the water quality measurement result by the above-described measurement of amylase activity or ORP. The addition amount and the number of additions are, for example, 2 to 50 mg / L and 1 to 48 times / day.
スライムコントロール剤の添加場所は、特に限定されないが、古紙原料や、澱粉を添加したり塗工したりしたものの製品として出荷できなかった工程損紙などの澱粉を多く含む原料スラリーにスライムコントロール剤が含まれるように添加する必要がある。原料スラリーへの添加後の後工程までスライムコントロール効果を維持できない場合には、上記水質測定結果に基づいて適宜スライムコントロール剤を追加添加することができるが、この場合、添加場所は製造工程全域で澱粉分解が抑制されるように設定する。 The place where the slime control agent is added is not particularly limited, but the slime control agent is added to the raw material slurry containing a large amount of starch, such as waste paper raw materials and process waste paper that has been added or coated with starch, but could not be shipped as a product. It must be added to be included. If the slime control effect cannot be maintained until the subsequent step after addition to the raw slurry, an additional slime control agent can be added as appropriate based on the results of the water quality measurement. Set so that starch degradation is suppressed.
２．吸着工程
本工程は、製紙工程水中に分散している澱粉を特異的に吸着して集める工程である。本工程では、製紙工程水中に分散している澱粉を吸着するため、製紙工程水に有機系微粒子を添加する。有機系微粒子の添加により、製紙工程水中に分散している澱粉が有機系微粒子に吸着され、集められる。
2. Adsorption process This process is a process of specifically adsorbing and collecting starch dispersed in papermaking process water. In this step, organic fine particles are added to the papermaking process water in order to adsorb the starch dispersed in the papermaking process water. By adding the organic fine particles, starch dispersed in the papermaking process water is adsorbed and collected by the organic fine particles.
有機系微粒子には、カチオン性官能基、アニオン性官能基又は水素結合能を持つ官能基を有する有機系微粒子であって、実質的に水不溶性の微粒子を用いる。 As the organic fine particles, organic fine particles having a cationic functional group, an anionic functional group, or a functional group having a hydrogen bonding ability and substantially water-insoluble fine particles are used.
カチオン性官能基としては、一級アミン、二級アミン、三級アミン及びこれらの酸塩や、四級アンモニウム基等の官能基を挙げることができる。また、アニオン性官能基としては、カルボキシル基、スルホン基、硫酸基、ホスホン酸基及びこれらのアルカリ金属塩、アルカリ土類金属塩等の官能基を挙げることができる。水素結合能を持つ官能基としては、カルボキシル基など上記のものの一部も含まれるが、水酸基、エステル基、アミド基、エーテル基などのノニオン基も挙げることができる。 Examples of the cationic functional group include primary amines, secondary amines, tertiary amines and acid salts thereof, and functional groups such as a quaternary ammonium group. Examples of the anionic functional group include a carboxyl group, a sulfone group, a sulfuric acid group, a phosphonic acid group, and functional groups such as alkali metal salts and alkaline earth metal salts thereof. Examples of the functional group having a hydrogen bonding ability include some of the above-described groups such as a carboxyl group, but also include nonionic groups such as a hydroxyl group, an ester group, an amide group and an ether group.
有機系微粒子のイオン性は、製紙工程水中の澱粉のイオン性に応じて選択してもよい。なお、通常の澱粉はアニオン性もしくはノニオン性であり、このような場合にはカチオン性の官能基を有する有機系微粒子を適用することが望ましい。 The ionicity of the organic fine particles may be selected according to the ionicity of the starch in the papermaking process water. Note that ordinary starch is anionic or nonionic, and in such a case, it is desirable to apply organic fine particles having a cationic functional group.
有機系微粒子としては、架橋構造を有する電解質ポリマーが好適である。電解質ポリマーは、架橋構造構成モノマー単位として、アニオン系であれば、アクリル酸、メタアクリル酸、マレイン酸、イタコン酸、ビニルスルホン酸、2−アクリルアミド−2−メチルプロパンスルホン酸、スチレンスルホン酸等、及びこれらのアルカリ金属塩等のアニオン性モノマーが挙げられる。また、ノニオン系であれば、ポリ（メタ）アクリルアミド、N−イソプロピルアクリルアミド、N−メチルアクリルアミド、N，N−ジメチルアクリルアミド、アクリロニトリル、スチレン、メチルもしくはエチル（メタ）アクリレート等のノニオン性モノマーが挙げられる。カチオン系であれば、ジメチルアミノエチル（メタ）アクリレ−トもしくはその四級アンモニウム塩やジメチルアミノプロピル（メタ）アクリルアミドもしくはその四級アンモニウム塩、ジアリルジメチルアンモニウムクロリド等のカチオン性モノマーが挙げられる。電解質ポリマーは、これらのモノマーのホモポリマーあるいはコポリマーとされる。 As the organic fine particles, an electrolyte polymer having a crosslinked structure is suitable. If the electrolyte polymer is an anionic polymer as a cross-linked structural monomer unit, acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, etc. And anionic monomers such as alkali metal salts thereof. Nonionic monomers such as poly (meth) acrylamide, N-isopropylacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, acrylonitrile, styrene, methyl or ethyl (meth) acrylate may be used as nonionic monomers. . If it is a cationic type, cationic monomers such as dimethylaminoethyl (meth) acrylate or a quaternary ammonium salt thereof, dimethylaminopropyl (meth) acrylamide or a quaternary ammonium salt thereof, diallyldimethylammonium chloride and the like can be mentioned. The electrolyte polymer is a homopolymer or copolymer of these monomers.
有機系微粒子を実質的に水に溶解しないようにするため、上記モノマーに加えて、架橋剤として、メチレンビスアクリルアミド、ジビニルベンゼンなどのジビニルモノマーをエマルション重合させることが好ましい。この場合、ジビニルモノマー量は全モノマーに対して０．０００１〜０．１モル％を加えればよい。この量を増減することによってポリマー微粒子の膨張度、つまり水中での粒子径を調整できる。 In order to prevent the organic fine particles from being substantially dissolved in water, it is preferable to emulsion-polymerize a divinyl monomer such as methylenebisacrylamide or divinylbenzene as a crosslinking agent in addition to the monomer. In this case, the amount of divinyl monomer should just add 0.0001-0.1 mol% with respect to all the monomers. By increasing or decreasing this amount, the degree of expansion of the polymer fine particles, that is, the particle diameter in water can be adjusted.
有機系微粒子は、炭化水素液体中に分散した状態で、又は希釈水に分散させて希釈された状態で、製紙工程水に添加する。有機系微粒子は、好ましくは逆相エマルションとして添加される。逆相エマルションとしては、有機系微粒子（Ｐ）と水（Ｗ）と、炭化水素液体（ＨＣ）と界面活性剤（Ｓ）とを含むものが好ましい。これら成分Ｐ、Ｗ、ＨＣ、Ｓの割合は、重量比（％）でＰ：Ｗ：ＨＣ：Ｓ＝20〜50：20〜40：20〜40：2〜20であり、ＰとＷの合計量が全体重量に対して40〜80重量％であることが好ましい。 The organic fine particles are added to the papermaking process water in a state of being dispersed in a hydrocarbon liquid or in a state of being diluted by being dispersed in dilution water. The organic fine particles are preferably added as a reverse phase emulsion. The reverse phase emulsion is preferably one containing organic fine particles (P), water (W), hydrocarbon liquid (HC) and surfactant (S). The ratio of these components P, W, HC, S is P: W: HC: S = 20-50: 20-40: 20-40: 2-20 in weight ratio (%), and the total of P and W The amount is preferably 40 to 80% by weight relative to the total weight.
炭化水素液体としては、脂肪族系の炭化水素液体が好適であり、具体的にはイソヘキサンなどのイソパラフィン、n−ヘキサン、ケロシン、鉱物油などが挙げられるが、これらに限定されるものではない。 As the hydrocarbon liquid, an aliphatic hydrocarbon liquid is suitable, and specific examples include isoparaffins such as isohexane, n-hexane, kerosene, and mineral oil, but are not limited thereto.
また、界面活性剤としては、例えばHLB ７〜１０の高級脂肪族（C10〜20）アルコールのポリオキシエチレンエーテル、もしくは高級脂肪酸（C10〜22）のポリオキシエチレンエステルが好適である。前者の例としては、ラウリルアルコール、セチルアルコール、ステアリルアルコール、オレイルアルコールなどのポリオキシエチレン（EO付加モル数＝3〜10）エーテルが挙げられる。後者の例としては、ラウリン酸、パルミチン酸、ステアリン酸、オレイン酸などのポリオキシエチレン（EO付加モル数＝3〜10）エステルが挙げられる。ただし、界面活性剤はこれらに限定されない。 Moreover, as surfactant, the polyoxyethylene ether of higher aliphatic (C10-20) alcohol of HLB 7-10 or the polyoxyethylene ester of higher fatty acid (C10-22) is suitable, for example. Examples of the former include polyoxyethylene (EO addition mole number = 3 to 10) ethers such as lauryl alcohol, cetyl alcohol, stearyl alcohol and oleyl alcohol. Examples of the latter include polyoxyethylene (EO addition mole number = 3 to 10) esters such as lauric acid, palmitic acid, stearic acid, and oleic acid. However, the surfactant is not limited to these.
有機系微粒子の平均粒子径は、２００μm以下、好ましくは１〜１００μm、さらに好ましくは１〜１０μmである。粒径が小さいと比表面積が大きくなり、澱粉の吸着効率が向上する。なお、粒子径は、通常の散乱光方式、又は透過光方式等の粒度分布測定装置により測定される。 The average particle diameter of the organic fine particles is 200 μm or less, preferably 1 to 100 μm, more preferably 1 to 10 μm. When the particle size is small, the specific surface area is increased and the adsorption efficiency of starch is improved. The particle diameter is measured by a particle size distribution measuring device such as a normal scattered light method or a transmitted light method.
有機系微粒子の添加量は、製紙工程水中の澱粉濃度や性状に応じて変わるが、概ね固形分で０．１〜５g／L、特に０．５〜３g／L程度が好適である。 The amount of organic fine particles to be added varies depending on the starch concentration and properties in the papermaking process water, but is generally about 0.1 to 5 g / L, particularly about 0.5 to 3 g / L in terms of solid content.
本発明に係る製紙方法において、分解抑制工程と吸着工程の前後は特に限定されず、どちらが先であってもよく、同一のタイミングで行われてもよい。 In the papermaking method according to the present invention, before and after the decomposition suppressing step and the adsorption step are not particularly limited, and either may be performed first or may be performed at the same timing.
３．凝集工程
本工程は、製紙工程水中の澱粉をパルプ繊維に定着させて紙製品として歩留まらせて製紙工程水から除去する工程である。本工程では、澱粉を吸着した有機系微粒子を凝集させるため、製紙工程水に無機凝結剤、有機凝結剤又は有機高分子凝集剤を添加する。無機凝結剤等の添加により、有機系微粒子に吸着された澱粉をパルプ繊維に定着させ、廃水中に澱粉が持ち込まれることを防止し、得られる紙製品の強度や印刷適性等の品質を高めることができる。
3. Aggregation step This step is a step of fixing the starch in the papermaking process water to the pulp fiber, yielding it as a paper product, and removing it from the papermaking process water. In this step, an inorganic coagulant, an organic coagulant, or an organic polymer coagulant is added to the papermaking process water in order to aggregate the organic fine particles adsorbing starch. By adding inorganic coagulant, etc., the starch adsorbed by organic fine particles is fixed to the pulp fiber, the starch is prevented from being brought into the wastewater, and the quality of the resulting paper product such as strength and printability is improved. Can do.
無機凝結剤としては、特に限定されず、例えば硫酸バンド、ポリ塩化アルミニウム、塩化第二鉄、硫酸第一鉄などから１以上を選定できる。無機凝結剤の添加量は、製紙工程水中の澱粉濃度とその性状に応じて変わるが、概ね固形分で５００〜５０００mg／L程度が好適である。 It does not specifically limit as an inorganic coagulant, For example, 1 or more can be selected from a sulfate band, polyaluminum chloride, ferric chloride, ferrous sulfate, etc. The amount of the inorganic coagulant added varies depending on the starch concentration in the papermaking process water and its properties, but is preferably about 500 to 5000 mg / L in terms of solid content.
有機凝結剤としては、特に限定されず、例えばポリエチレンイミン、ジアリルジメチルアンモニウムクロリド、エチレンジアミンエピクロルヒドリン重縮合物、ポリアルキレンポリアミンなどのカチオン性有機系ポリマーから１以上を選定できる。有機凝結剤の添加量は、製紙工程水中の澱粉濃度とその性状に応じて変わるが、概ね固形分で１〜１００mg／Lとすることができる。 The organic coagulant is not particularly limited, and for example, one or more can be selected from cationic organic polymers such as polyethyleneimine, diallyldimethylammonium chloride, ethylenediamine epichlorohydrin polycondensate, and polyalkylene polyamine. The amount of the organic coagulant added varies depending on the starch concentration in the papermaking process water and its properties, but can be generally 1 to 100 mg / L in solid content.
有機高分子凝集剤としては、特に限定されず、例えば、アニオン系であれば、ポリ（メタ）アクリル酸、（メタ）アクリル酸と（メタ）アクリルアミドの共重合物、及びこれらのアルカリ金属塩等が挙げられる。ノニオン系であれば、ポリ（メタ）アクリルアミド等が挙げられる。カチオン系であれば、ジメチルアミノエチル（メタ）アクリルアミドもしくはその四級アンモニウム塩やジメチルアミノプロピル（メタ）アクリルアミドもしくはその四級アンモニウム塩等のカチオン性モノマーからなるホモポリマー、あるいはこれらカチオン性モノマーと共重合可能なノニオン性モノマーとの共重合体が挙げられる。有機高分子凝集剤の添加量は、製紙工程水中の澱粉濃度とその性状に応じて変わるが、概ね固形分で１〜１００mg／Lとすることができる。 The organic polymer flocculant is not particularly limited and, for example, poly (meth) acrylic acid, a copolymer of (meth) acrylic acid and (meth) acrylamide, and alkali metal salts thereof, etc. Is mentioned. If it is nonionic, poly (meth) acrylamide etc. are mentioned. In the case of a cationic system, homopolymers composed of cationic monomers such as dimethylaminoethyl (meth) acrylamide or a quaternary ammonium salt thereof, dimethylaminopropyl (meth) acrylamide or a quaternary ammonium salt thereof, or a copolymer with these cationic monomers. Examples thereof include a copolymer with a polymerizable nonionic monomer. The amount of the organic polymer flocculant added varies depending on the starch concentration in the papermaking process water and its properties, but can be generally 1 to 100 mg / L in solid content.
無機凝結剤、有機凝結剤及び有機高分子凝集剤は、いずれか１種を添加すればよいが、凝結剤と凝集剤を組み合わせて使用するのが好適であり、添加順序は凝結剤を添加してよく反応させた後、凝集剤を添加することが好ましい。 Any one of inorganic coagulant, organic coagulant and organic polymer coagulant may be added, but it is preferable to use a combination of coagulant and coagulant, and the order of addition is to add coagulant. It is preferable to add a flocculant after thoroughly reacting.
以下、本発明を実施例に基づいて説明するが、本発明はかかる実施例のみに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited only to this Example.
（１）試験用パルプスラリーの調製
31g/kgで澱粉を含有する段ボール古紙330gを水道水15Lに分散させ、ビーターで離解、叩解を行い、固形分で2重量％のパルプスラリー（CSF＝315ml）を調製した。この2重量％のパルプスラリー15Lに5重量％澱粉水溶液600mlを添加して試験用パルプスラリーとした。澱粉には、キシダ化学製試薬特級を使用した。コロイド当量測定によるアニオン化度は、−0.15meq/gで若干アニオン性を示した。澱粉は、ホットプレートスターラーにて加熱溶解し、5重量％澱粉水溶液として調製した。
(1) Preparation of test pulp slurry
Dissolved 330 g of corrugated used paper containing starch at 31 g / kg in 15 L of tap water, disaggregated and beaten with a beater to prepare a pulp slurry (CSF = 315 ml) having a solid content of 2% by weight. 600 ml of a 5% by weight starch aqueous solution was added to 15 L of this 2% by weight pulp slurry to obtain a test pulp slurry. For the starch, a special grade reagent manufactured by Kishida Chemical was used. The degree of anionization by colloidal equivalent measurement was −0.15 meq / g, indicating a little anionic property. The starch was heated and dissolved with a hot plate stirrer to prepare a 5% by weight starch aqueous solution.
（２）手抄紙の調製
試験用パルプスラリーから、JIS P 8029規定の方法に準拠して、坪量120g/m2の手抄紙を調製した。
(2) Preparation of handmade paper Handmade paper having a basis weight of 120 g / m 2 was prepared from the test pulp slurry in accordance with the method defined in JIS P 8029.
（３）水中澱粉濃度・アミラーゼ活性・COD（Mn）の測定
製紙工程水を５A濾紙で吸引濾過した濾液3.2mlに10倍希釈塩酸4 ml、0.002Ｎヨウ素溶液0.4 ml、純水0.4 mlを加えて、分光光度計を用いて580nmの吸光度を測定し、既知濃度の澱粉サンプルから作成した検量線から澱粉濃度を算出した。また、濾液について、市販のアミラーゼ測定キット（Megazyme International Ireland社製）を用いてアミラーゼ活性を測定した。COD（Mn）の測定は、製紙工程水の上澄み液を用いて、JIS K 0102に記載の100℃における測定法に準拠して行なった。
(3) Measurement of starch concentration in water, amylase activity, and COD (Mn) Add 10 ml diluted hydrochloric acid 4 ml, 0.002N iodine solution 0.4 ml, and pure water 0.4 ml to 3.2 ml of filtrate obtained by suction filtration of papermaking process water with 5A filter paper. Then, the absorbance at 580 nm was measured using a spectrophotometer, and the starch concentration was calculated from a calibration curve prepared from starch samples having a known concentration. Further, the amylase activity of the filtrate was measured using a commercially available amylase measurement kit (manufactured by Megazyme International Ireland). The measurement of COD (Mn) was performed in accordance with the measurement method at 100 ° C. described in JIS K 0102, using the supernatant of the papermaking process water.
（４）紙中澱粉濃度と紙の強度の測定
手抄紙1.0ｇを純水50mlに浸し、これを90℃の温浴中で30分間静置して、紙中に含まれる澱粉を熱水抽出し、上記の測定法に従って紙中澱粉濃度を算出した。また、手抄紙を用いて、JIS P 8112規定の方法に準拠して破裂強さを測定した。
(4) Measurement of starch concentration in paper and paper strength Immerse 1.0 g of handmade paper in 50 ml of pure water and leave it in a 90 ° C warm bath for 30 minutes to extract the starch contained in the paper with hot water. The starch concentration in the paper was calculated according to the above measurement method. Also, burst strength was measured using handmade paper in accordance with the method defined in JIS P8112.
（５）スライムコントロール剤の調製
硫酸アンモニウムと次亜塩素酸ソーダとを１：１（モル比）で混合し、塩素換算濃度1000mg/Lのスライムコントロール剤を調製した。
(5) Preparation of slime control agent Ammonium sulfate and sodium hypochlorite were mixed at 1: 1 (molar ratio) to prepare a slime control agent having a chlorine conversion concentration of 1000 mg / L.
（６）有機系微粒子の調製
有機系微粒子としてジメチルアミノエチルアクリレートの塩化メチル四級化物／アクリルアミド＝60／40（モル％）コポリマーの架橋ゲル微粒子（平均粒径15μm）を含むものを用いて、逆相エマルションを調製した。
(6) Preparation of organic fine particles Organic fine particles containing crosslinked gel fine particles (average particle size 15 μm) of dimethylaminoethyl acrylate methyl chloride quaternized / acrylamide = 60/40 (mol%) copolymer, A reverse emulsion was prepared.
架橋ゲル微粒子の製造は以下の手順で行った。攪拌器、ジムロート冷却管、窒素導入管、温度計を備えた1L 4つ口セパラブルフラスコを用意し、窒素雰囲気下、HLB＝9.5の高級アルコールポリオキシエチレンエーテル48gを混合したケロシン123gをフラスコに入れる。窒素雰囲気下で強く攪拌しながら、ジメチルアミノエチルアクリレートの塩化メチル四級化物（65％）178gとアクリルアミド28gと、メチレンビスアクリルアミド0.01gと水82gの混合物をゆっくりフラスコに投入する。フラスコ内を50℃に保ち、そこに開始剤としてアゾビスイソブチロニトリルのアセトン10％溶液0.65gを添加して、50℃のまま8時間窒素雰囲気下、攪拌しながら重合を行う。その反応物として、水に入れても溶解しない不溶性の微粒子ゲルを製造した。有機系微粒子ゲルの成分は、ポリマー50重量％、水50重量％である。有機系微粒子ゲル分散液の組成は、ポリマー31重量％、水31重量％、ケロシン27重量％、界面活性剤11重量％であった。 The crosslinked gel fine particles were produced by the following procedure. Prepare a 1L 4-neck separable flask equipped with a stirrer, Dimroth condenser, nitrogen inlet tube, and thermometer. In a nitrogen atmosphere, add 123g of kerosene mixed with 48g of higher alcohol polyoxyethylene ether of HLB = 9.5 to the flask. Put in. While stirring vigorously under a nitrogen atmosphere, a mixture of 178 g of methyl chloride quaternized dimethylaminoethyl acrylate (65%), 28 g of acrylamide, 0.01 g of methylenebisacrylamide and 82 g of water is slowly added to the flask. The inside of the flask is kept at 50 ° C., and 0.65 g of a 10% solution of azobisisobutyronitrile in acetone is added as an initiator, and polymerization is carried out while stirring at 50 ° C. for 8 hours in a nitrogen atmosphere. As the reaction product, an insoluble fine particle gel that does not dissolve even in water was produced. The components of the organic fine particle gel are 50% by weight of polymer and 50% by weight of water. The composition of the organic fine particle gel dispersion was 31% by weight of polymer, 31% by weight of water, 27% by weight of kerosene, and 11% by weight of surfactant.
（７）有機高分子凝結剤の調製
カチオン性の高分子凝集剤としてジメチルアミノエチル（メタ）アクリレートの四級アンモニウム塩／アクリルアミドの60／40（モル％）の共重合物を使用した。
(7) Preparation of organic polymer coagulant A 60/40 (mol%) copolymer of dimethylaminoethyl (meth) acrylate quaternary ammonium salt / acrylamide was used as a cationic polymer flocculant.
[実験例]
試験用パルプスラリーを30℃で3日間静置したサンプル、及び試験用パルプスラリーに１回/日の頻度でスライムコントロール剤を20mg/L添加して30℃で3日間静置したサンプルを調製した。それぞれのサンプルの分析結果を「表１」に示す。
[Experimental example]
A sample was prepared by allowing the test pulp slurry to stand at 30 ° C. for 3 days, and a sample in which 20 mg / L of slime control agent was added to the test pulp slurry at a frequency of once / day and allowed to stand at 30 ° C. for 3 days. . The analysis results of each sample are shown in “Table 1”.
スライムコントロール剤処理を行わないと微生物が増殖し、ORP値の低下とアミラーゼ活性の上昇が見られる。 Without treatment with the slime control agent, microorganisms grow, and a decrease in ORP value and an increase in amylase activity are observed.
スライムコントロール剤処理の有無で3日間静置した「表１」のサンプルを用いて、有機系微粒子及び有機系高分子凝集剤の添加による効果を評価した。スライムコントロール剤処理を行なったサンプルを用いた分析結果を「表２」に、スライムコントロール剤処理を行なわなかったサンプルを用いた分析結果を「表３」に示す。 Using the samples shown in Table 1 that were allowed to stand for 3 days with or without treatment with a slime control agent, the effects of the addition of organic fine particles and organic polymer flocculants were evaluated. The analysis results using the samples subjected to the slime control agent treatment are shown in “Table 2”, and the analysis results using the samples not subjected to the slime control agent treatment are shown in “Table 3”.
「表２」中、実施例１及び実施例２に示す通り、スライムコントロール剤処理を行って微生物由来のアミラーゼによる澱粉分解を抑制した上、澱粉を有機系微粒子により吸着し、手抄紙に定着させることで、水中の澱粉量及びCODを低減できた。また、得られる手抄紙中の澱粉量を増加させ、手抄紙の強度を向上させることができた。 As shown in Example 1 and Example 2 in Table 2, the slime control agent treatment was performed to suppress starch degradation by amylase derived from microorganisms, and the starch was adsorbed by organic fine particles and fixed on handmade paper. As a result, the amount of starch and COD in water could be reduced. In addition, the amount of starch in the resulting handmade paper was increased, and the strength of the handmade paper could be improved.
本発明に係る製紙方法によれば、廃水に持ち込まれる澱粉量を低減して、廃水中の澱粉及び澱粉分解物に由来する有機物成分を減少させることで、廃水のCODを低減することができる。このため、本発明は、紙の製造工程における用水原価の削減や、加温された製紙工程水の系外流出防止による省エネルギーに寄与できる。 According to the papermaking method of the present invention, the COD of wastewater can be reduced by reducing the amount of starch brought into wastewater and reducing organic components derived from starch and starch degradation products in wastewater. For this reason, this invention can contribute to the energy saving by the reduction of the water cost in the manufacturing process of paper, and prevention of the outflow of the heated papermaking process water.
また、本発明に係る製紙方法によれば、製紙工程水中の澱粉を紙製品に歩留まらせることで、紙製品の強度を向上させ、新たに添加する澱粉や紙力増強剤の量を削減することもできる。 In addition, according to the papermaking method of the present invention, the starch in the papermaking process water is allowed to yield on the paper product, thereby improving the strength of the paper product and reducing the amount of newly added starch and paper strength enhancer. You can also.
Claims (2)
前記製紙工程水に、カチオン性官能基、アニオン性官能基又は水素結合能を持つ官能基を有する実質的に水不溶性の有機系微粒子を添加する工程と、
有機系微粒子の添加後の製紙工程水に、無機凝結剤、有機凝結剤及び有機高分子凝集剤から選択される１以上を添加する工程と、を含む製紙方法。 Adding a slime control agent to papermaking process water containing starch;
Adding substantially water-insoluble organic fine particles having a cationic functional group, an anionic functional group or a functional group having a hydrogen bonding ability to the papermaking process water;
And a step of adding one or more selected from an inorganic coagulant, an organic coagulant and an organic polymer flocculant to the papermaking process water after the addition of the organic fine particles.
前記製紙工程水に、カチオン性官能基、アニオン性官能基又は水素結合能を持つ官能基を有する実質的に水不溶性の有機系微粒子を添加する手段と、
澱粉吸着工程後の製紙工程水に、無機凝結剤、有機凝結剤及び有機高分子凝集剤から選択される１以上を添加する手段と、を備える製紙装置。
Means for adding a slime control agent to papermaking process water containing starch;
Means for adding substantially water-insoluble organic fine particles having a cationic functional group, an anionic functional group or a functional group having hydrogen bonding ability to the papermaking process water;
Means for adding one or more selected from an inorganic coagulant, an organic coagulant, and an organic polymer flocculant to the papermaking process water after the starch adsorption step.
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